WO2017057553A1

WO2017057553A1 - Laminated body

Info

Publication number: WO2017057553A1
Application number: PCT/JP2016/078790
Authority: WO
Inventors: 前中　寛; 靖乾
Original assignee: 積水化学工業株式会社
Priority date: 2015-09-30
Filing date: 2016-09-29
Publication date: 2017-04-06
Also published as: EP3339021A4; CN113059875A; CN113059875B; US10477671B2; KR20180027599A; JP2018019104A; CN113733688A; JP6235733B2; KR101887337B1; CN108136734A; TW201729998A; US20180302976A1; EP3339021B1; JPWO2017057553A1; EP3339021A1; TWI738670B

Abstract

Provided is a laminated body capable of lowering thermal resistance and capable of suppressing peeling after a cooling/heating cycle. The laminated body according to the present invention is provided with an insulating resin layer, a first metal material that is a metal foil or a metal plate and a second metal material that is a metal foil or a metal plate, wherein the first metal material is laminated on a first surface of the insulating resin layer and the second metal material is laminated on a second surface of the insulating resin layer that is opposite the first surface, the thickness of the insulating resin layer is at most 200 μm, the total thickness of the first metal material and the second metal material is no less than 200 μm, the ratio of the thickness of the first metal material to the thickness of the second metal material is 0.2-5 and the ratio of the surface area of the surface of the first metal material that is opposite the insulating resin layer side to the surface area of the surface of the second metal material that is opposite the insulating resin layer side is 0.5-2.

Description

Laminated body

The present invention relates to a laminate including an insulating resin layer and a metal foil or a metal plate.

A laminate in which a metal foil or a metal plate is laminated on one side or both sides of an insulating resin layer is known. Such a laminate is used, for example, in a heat generating device such as a light emitting diode (LED) device or a power semiconductor, a module including the heat generating device, and the like in order to suppress a temperature rise during use.

The following Patent Document 1 discloses a laminate including an insulating resin layer and a copper foil or a copper plate integrated on both surfaces of the insulating resin layer. The insulating resin layer has a thermal conductivity of 4 W / m · K or more. The total thickness of both the copper foil or the copper plate integrated on both surfaces of the insulating resin layer is 600 μm or more.

Patent Document 2 below discloses a laminate comprising a ceramic substrate and a metal plate bonded to both surfaces of the ceramic substrate via a silver-copper brazing filler metal layer. In this laminate, a ceramic substrate is disposed between two metal plates instead of an insulating resin layer.

JP 2006-76263 A JP 2014-118310 A

In the laminate described in Patent Document 1, the thermal resistance cannot be lowered, or the peeling after the thermal cycle cannot be suppressed. In all of the laminates shown in the examples and comparative examples of Patent Document 1, both a sufficiently low thermal resistance and a sufficiently excellent anti-peeling property after a cooling / heating cycle are not achieved.

Further, as described in Patent Document 2, when a ceramic substrate is used, there is a problem that peeling is likely to occur after a thermal cycle because the linear expansion coefficient of the ceramic substrate is considerably low.

An object of the present invention is to provide a laminate that can reduce thermal resistance and can suppress peeling after a cooling and heating cycle.

In a wide aspect of the present invention, an insulating resin layer, a first metal material that is a metal foil or a metal plate, and a second metal material that is a metal foil or a metal plate, the first metal material is Laminated on the first surface of the insulating resin layer, and the second metal material is laminated on a second surface opposite to the first surface of the insulating resin layer, The thickness of the insulating resin layer is 200 μm or less, the total thickness of the first metal material and the second metal material is 200 μm or more, and the thickness of the first metal material is the second metal. The ratio to the thickness of the material is 0.2 or more and 5 or less, and the surface area of the surface opposite to the insulating resin layer side of the first metal material is the insulating resin layer side of the second metal material A laminate having a ratio of the surface to the surface area opposite to that of 0.5 to 2 is provided.

In a specific aspect of the laminate according to the present invention, a ratio of a linear expansion coefficient of the insulating resin layer to a linear expansion coefficient of the first metal material is 0.5 or more and 2 or less, and the insulating resin The ratio of the linear expansion coefficient of the layer to the linear expansion coefficient of the second metal material is 0.5 or more and 2 or less.

In a specific aspect of the laminate according to the present invention, the insulating resin layer has an elastic modulus at 25 ° C. of 1 GPa or more and 50 GPa or less.

In a specific aspect of the laminate according to the present invention, the side surface of the first metal material is inclined inwardly toward the surface side opposite to the insulating resin layer side.

In a specific aspect of the laminate according to the present invention, the side surface of the second metal material is inclined inwardly toward the surface side opposite to the insulating resin layer side.

In a specific aspect of the laminate according to the present invention, the first metal material is a circuit.

In a specific aspect of the laminate according to the present invention, there is an insulating resin layer portion where the first metal material is not laminated, and the surface of the first metal material opposite to the insulating resin layer side is present. The arithmetic average roughness Ra is 2 μm or less, and the arithmetic average roughness Ra of the surface of the first metal material on the insulating resin layer side is 0.1 μm or more.

In a specific aspect of the laminate according to the present invention, the surface area of the surface of the first metal material on the side of the insulating resin layer is the surface area of the surface opposite to the side of the insulating resin layer of the first metal material. The ratio to is 0.8 or more and less than 1.0.

In a specific aspect of the laminate according to the present invention, the first metal material is a circuit, and the second metal material is a circuit.

In a specific aspect of the laminate according to the present invention, there is an insulating resin layer portion where the second metal material is not laminated, and the surface of the second metal material opposite to the insulating resin layer side is present. The arithmetic average roughness Ra is 2 μm or less, and the arithmetic average roughness Ra of the surface of the second metal material on the insulating resin layer side is 0.1 μm or more.

In a specific aspect of the laminate according to the present invention, the surface area of the surface of the second metal material opposite to the side of the insulating resin layer, the surface area of the surface of the second metal material on the side of the insulating resin layer. The ratio to is 0.8 or less.

In a specific aspect of the laminate according to the present invention, the glass transition temperature of the insulating resin layer is 150 ° C. or higher.

In a specific aspect of the laminate according to the present invention, the insulating resin layer is not a prepreg.

On the specific situation with the laminated body which concerns on this invention, the surface on the opposite side to the said insulating resin layer side of the said 1st metal material is exposed, or the said insulating resin layer of the said 1st metal material A protective film is laminated on the surface opposite to the side.

In a specific aspect of the laminate according to the present invention, the surface of the first metal material opposite to the insulating resin layer side is exposed.

In a specific aspect of the laminate according to the present invention, the insulating resin layer includes an inorganic filler.

The laminate according to the present invention includes an insulating resin layer, a first metal material that is a metal foil or a metal plate, and a second metal material that is a metal foil or a metal plate, and the first metal material is , Laminated on the first surface of the insulating resin layer, and the second metal material is laminated on a second surface opposite to the first surface of the insulating resin layer, The thickness of the insulating resin layer is 200 μm or less, the total thickness of the first metal material and the second metal material is 200 μm or more, and the thickness of the first metal material is the second The ratio of the metal material to the thickness is 0.2 or more and 5 or less, and the surface area of the surface opposite to the insulating resin layer side of the first metal material is the insulating resin layer of the second metal material. Since the ratio of the surface to the surface opposite to the side is 0.5 or more and 2 or less, the thermal resistance can be lowered. , Peeling after the cooling and heating cycle can be suppressed.

FIG. 1 is a cross-sectional view showing a laminated body according to the first embodiment of the present invention. FIG. 2 is a cross-sectional view showing a laminate according to the second embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The laminate according to the present invention includes an insulating resin layer, a first metal material, and a second metal material. The first metal material is a metal foil or a metal plate. The second metal material is a metal foil or a metal plate.

In the laminate according to the present invention, the first metal material is laminated on the first surface (one surface) of the insulating resin layer, and the second metal material is the insulating resin layer. Are stacked on the second surface (the other surface) opposite to the first surface.

In the laminate according to the present invention, the insulating resin layer has a thickness of 200 μm or less. In the laminated body according to the present invention, the total thickness of the first metal material and the second metal material is 200 μm or more. In the laminated body according to the present invention, the ratio of the thickness of the first metal material to the thickness of the second metal material (the thickness of the first metal material / the thickness of the second metal material) is 0.2. It is 5 or less. In the laminate according to the present invention, the ratio of the surface area of the surface opposite to the insulating resin layer side of the first metal material to the surface area of the surface opposite to the insulating resin layer side of the second metal material. The surface area of the surface opposite to the insulating resin layer side of the first metal material / the surface area of the surface opposite to the insulating resin layer side of the second metal material is 0.5 or more and 2 or less.

In the present invention, since the above-described configuration is provided, the thermal resistance can be lowered, and peeling after the thermal cycle can be suppressed.

Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view showing a laminated body according to the first embodiment of the present invention.

1 includes an insulating resin layer 11, a first metal material 12, and a second metal material 13. The first metal material 12 is a metal foil or a metal plate. The second metal material 13 is a metal foil or a metal plate.

The first metal material 12 is laminated on the first surface (one surface) of the insulating resin layer 11. The second metal material 13 is laminated on the second surface (the other surface) of the insulating resin layer 11. In the present embodiment, the first metal material 12 and the second metal material 13 are circuits. The first metal material 12 and the second metal material 13 are formed in partial regions on each of the first surface and the second surface of the insulating resin layer 11. The first metal material and the second metal material may be formed in a partial region on at least one of the first surface and the second surface of the insulating resin layer. In the present embodiment, the side surface of the first metal material 12 is inclined inwardly toward the surface side opposite to the insulating resin layer 11 side, and the side surface of the second metal material 13 is inclined to the insulating resin layer. It inclines inside as it goes to the surface side opposite to the 11th side. In the laminated body 1, there is an insulating resin layer 11 portion where the first metal material 12 is not laminated. In the laminated body, there may be an insulating resin layer portion where the first metal material is not laminated. In the laminate 1, there is an insulating resin layer 11 portion where the second metal material 13 is not laminated. In the laminated body, there may be an insulating resin layer portion where the second metal material is not laminated.

FIG. 2 is a cross-sectional view showing a laminate according to the second embodiment of the present invention.

In the laminate 1 shown in FIG. 1, the first metal material 12 and the second metal material 13 are formed in partial regions on each of the first surface and the second surface of the insulating resin layer 11. Yes. In the laminated body 1A shown in FIG. 2, the first metal material 12 is formed in a partial region on the first surface of the insulating resin layer 11, and is a circuit. In the laminated body 1A, the second metal material 13A is formed in the entire region on the second surface of the insulating resin layer 11, and no circuit is formed. Thus, for example, the second metal material may be formed in the entire region on the second surface, may not be formed with a circuit, or may be a metal material before circuit formation. .

The thickness of the insulating resin layer 11 is 200 μm or less. The total thickness of the first metal material 12 and the second metal material 13 is 200 μm or more. The ratio (thickness of the first metal material 12 / thickness of the second metal material 13) is 0.2 or more and 5 or less. The ratio (surface area of the surface opposite to the insulating resin layer 11 side of the first metal material 12 / surface area of the surface opposite to the insulating resin layer 11 side of the second metal material 13) is 0.5 or more, 2 It is as follows.

In the laminate, it is preferable that the first metal material, the insulating resin layer, and the second metal material are integrated.

The thickness of the insulating resin layer is 200 μm or less. From the viewpoint of effectively reducing the thermal resistance and effectively suppressing peeling after the cooling and heating cycle, the thickness of the insulating resin layer is preferably 150 μm or less, more preferably 100 μm or less. From the viewpoint of enhancing the insulation reliability, the thickness of the insulating resin layer is preferably 40 μm or more, more preferably 60 μm or more. The thickness of the insulating resin layer is an average of the entire thickness of the insulating resin layer.

The total thickness of the first metal material and the second metal material is 200 μm or more. From the viewpoint of effectively improving heat dissipation, the total thickness of the first metal material and the second metal material is preferably 400 μm or more. From the viewpoint of lightness and handleability, the total thickness of the first metal material and the second metal material is preferably 2 mm or less.

The ratio (the thickness of the first metal material / the thickness of the second metal material) is 0.2 or more and 5 or less. From the viewpoint of effectively reducing the thermal resistance and effectively suppressing the peeling after the cooling and heating cycle, the above ratio (the thickness of the first metal material / the thickness of the second metal material) is preferably 0.00. It is 3 or more, more preferably 0.6 or more, still more preferably 0.8 or more, preferably 3 or less, more preferably 1.6 or less, and still more preferably 1.2 or less. The thickness of the first metal material is an average of the total thickness of the first metal material. The thickness of the second metal material is an average of the total thickness of the second metal material.

The thickness of the insulating resin layer, the thickness of the first metal material, and the thickness of the second metal material were determined by observing the cross section of the laminate with, for example, a microscope (such as “VHX-5000” manufactured by Keyence Corporation). It can be evaluated by measuring.

The ratio (surface area of the surface opposite to the insulating resin layer side of the first metal material / surface area of the surface opposite to the insulating resin layer side of the second metal material) is 0.5 or more and 2 or less. . From the viewpoint of effectively reducing the thermal resistance and effectively suppressing peeling after the thermal cycle, the above ratio (surface area of the first metal material opposite to the insulating resin layer side / second metal) The surface area of the surface opposite to the insulating resin layer side of the material is preferably 0.6 or more, and preferably 1.67 or less.

The surface area can be measured, for example, by observing with an image size measuring instrument (“IM-6125” manufactured by Keyence Corporation).

From the viewpoint of effectively suppressing peeling after the thermal cycle, the ratio of the linear expansion coefficient of the insulating resin layer to the linear expansion coefficient of the first metal material (linear expansion coefficient of the insulating resin layer / first metal material). The linear expansion coefficient) is preferably 0.5 or more, more preferably 0.6 or more, preferably 2 or less, more preferably 1.8 or less.

From the viewpoint of effectively suppressing peeling after the thermal cycle, the ratio of the linear expansion coefficient of the insulating resin layer to the linear expansion coefficient of the second metal material (linear expansion coefficient of the insulating resin layer / second metal material). The linear expansion coefficient) is preferably 0.5 or more, more preferably 0.6 or more, preferably 2 or less, more preferably 1.8 or less.

From the viewpoint of effectively suppressing peeling after the thermal cycle, the linear expansion coefficient of the insulating resin layer is preferably 5 ppm / ° C. or more, more preferably 10 ppm / ° C. or more, preferably 35 ppm / ° C. or less, more preferably 30 ppm. / ° C or less.

The linear expansion coefficient is measured using a thermomechanical analyzer under conditions from 25 ° C. to the glass transition temperature. Examples of the thermomechanical analyzer include “TMA-60” manufactured by Shimadzu Corporation.

From the viewpoint of effectively suppressing peeling after the thermal cycle, the elastic modulus at 25 ° C. of the insulating resin layer is preferably 1 GPa or more, more preferably 5 GPa or more, preferably 50 GPa or less, more preferably 20 GPa or less.

The above elastic modulus is measured at 25 ° C. using a dynamic viscoelasticity measuring device. Examples of the dynamic viscoelasticity measuring apparatus include “DMS6100” manufactured by Hitachi High-Tech Science Co., Ltd.

From the viewpoint of further suppressing peeling, it is preferable that the side surface of the first metal material is inclined inwardly toward the surface side opposite to the insulating resin layer side. From the viewpoint of further suppressing peeling, it is preferable that the side surface of the second metal material is inclined inwardly toward the surface side opposite to the insulating resin layer side.

In order to incline inwardly as the side surface of the first metal material moves toward the surface side opposite to the insulating resin layer side, for example, the etching amount when etching the metal material can be adjusted. .

The first metal material may be laminated on the entire first surface of the insulating resin layer, or may be laminated on a partial region of the first surface of the insulating resin layer. The second metal material may be laminated on the entire second surface of the insulating resin layer, or may be laminated on a partial region of the second surface of the insulating resin layer.

From the viewpoint of further improving heat dissipation, the arithmetic average roughness Ra of the surface of the first metal material opposite to the insulating resin layer side is preferably 2 μm or less, more preferably 1 μm or less. The arithmetic mean roughness Ra of the surface opposite to the insulating resin layer side of the first metal material may be 0 μm. From the viewpoint of further improving the heat dissipation, the arithmetic average roughness Ra of the surface of the second metal material opposite to the insulating resin layer side is preferably 2 μm or less, more preferably 1 μm or less. The arithmetic average roughness Ra of the surface of the second metal material opposite to the insulating resin layer side may be 0 μm.

From the viewpoint of further improving the adhesion stability, the arithmetic average roughness Ra of the surface of the first metal material on the insulating resin layer side is preferably 0.1 μm or more, more preferably 0.2 μm or more. From the viewpoint of further improving the adhesion stability, the arithmetic average roughness Ra of the surface of the second metal material on the insulating resin layer side is preferably 0.1 μm or more, more preferably 0.2 μm or more.

The arithmetic average roughness Ra is measured according to JIS B0601: 1994. Specifically, the arithmetic average roughness Ra is measured as follows.

The arithmetic average roughness Ra is measured at a moving speed of 0.6 mm using a surface roughness meter (“Surfcom Flex” manufactured by Tokyo Seimitsu Co., Ltd.).

Ratio of the surface area of the surface of the first metal material opposite to the insulating resin layer side to the surface area of the surface of the first metal material on the insulating resin layer side (insulating resin layer side of the first metal material) The surface area opposite to the surface area / the surface area of the surface of the first metal material on the insulating resin layer side) may be greater than 1 or 1. From the viewpoint of further suppressing peeling and maintaining good heat dissipation, the above ratio (surface area opposite to the insulating resin layer side of the first metal material / insulating resin layer side of the first metal material) The surface area) is preferably 0.8 or more, preferably less than 1. Ratio of the surface area of the surface opposite to the insulating resin layer side of the second metal material to the surface area of the surface of the second metal material on the insulating resin layer side (insulating resin layer side of the second metal material) The surface area opposite to the surface area / the surface area of the surface of the second metal material on the insulating resin layer side) may be greater than 1 or 1. From the viewpoint of further suppressing peeling and maintaining good heat dissipation, the above ratio (surface area opposite to the insulating resin layer side of the second metal material / insulating resin layer side of the second metal material) The surface area) is preferably 0.8 or more, preferably less than 1.

From the viewpoint of further improving the heat resistance and further suppressing the peeling after the cooling and heating cycle, the glass transition temperature of the insulating resin layer is preferably 150 ° C. or higher, more preferably 180 ° C. or higher. The higher the glass transition temperature, the better, and the upper limit of the glass transition temperature is not particularly limited.

The glass transition temperature is measured at a rate of temperature increase of 5 ° C./min using a dynamic viscoelasticity measuring device (“DMS6100” manufactured by Hitachi High-Tech Science Co., Ltd.).

The insulating resin layer may be a prepreg or not a prepreg. From the viewpoint of further improving heat dissipation and insulation, the insulating resin layer is preferably not a prepreg. In the prepreg, generally, a nonwoven fabric is impregnated with an insulating resin. The nonwoven fabric may be a glass cloth.

In the laminate, the surface of the first metal material opposite to the insulating resin layer side is exposed, or the surface of the first metal material opposite to the insulating resin layer side is exposed. It is preferable that the protective film is laminated. In the laminate, the surface of the first metal material opposite to the insulating resin layer side is exposed, or the surface of the first metal material opposite to the insulating resin layer side is exposed. It can be used in the state where the protective film is laminated. In addition, after such a laminated body is incorporated in an electronic component, another electronic component member may be laminated on the surface of the first metal material opposite to the insulating resin layer side. In the laminate, the surface of the second metal material opposite to the insulating resin layer side is exposed, or the surface of the second metal material opposite to the insulating resin layer side is exposed. It is preferable that the protective film is laminated. In the laminate, the surface of the second metal material opposite to the insulating resin layer side is exposed, or the second metal material is protected on the surface opposite to the insulating resin layer side. It can be used in a state where films are laminated. In addition, after such a laminated body is incorporated in an electronic component, another electronic component member may be laminated on the surface of the second metal material opposite to the insulating resin layer side.

Hereinafter, other details of the laminate will be described.

(Insulating resin layer)
Examples of the material for the insulating resin layer include a curable compound (A) and a curing agent (B). The insulating resin layer is, for example, a cured product of a curable composition (insulating resin layer material) containing a curable compound and a thermosetting agent. Moreover, it is preferable that the material of the said insulating resin layer contains an inorganic filler (C). The insulating resin layer preferably contains an inorganic filler (C).

The curable compound (A) may be a curable compound (A1) having a molecular weight of less than 10,000, a curable compound (A2) having a molecular weight of 10,000 or more, and a molecular weight of less than 10,000. Both a certain curable compound (A1) and a curable compound (A2) having a molecular weight of 10,000 or more may be used. As for a sclerosing | hardenable compound (A), only 1 type may be used and 2 or more types may be used together.

Curable compound (A1):
Examples of the curable compound (A1) having a molecular weight of less than 10,000 include curable compounds having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The curable compound having a cyclic ether group is preferably a curable compound having an epoxy group or an oxetanyl group. As for a sclerosing | hardenable compound (A1), only 1 type may be used and 2 or more types may be used together.

The curable compound (A1) may contain an epoxy compound (A1a) having an epoxy group, or may contain an oxetane compound (A1b) having an oxetanyl group.

From the viewpoint of further improving the heat resistance and voltage resistance of the cured product, the curable compound (A1) preferably has an aromatic skeleton.

The aromatic skeleton is not particularly limited, and examples thereof include a naphthalene skeleton, a fluorene skeleton, a biphenyl skeleton, an anthracene skeleton, a pyrene skeleton, a xanthene skeleton, an adamantane skeleton, and a bisphenol A skeleton. A biphenyl skeleton or a fluorene skeleton is preferred. In this case, the thermal cycle resistance and heat resistance of the cured product are further enhanced.

Specific examples of the epoxy compound (A1a) having an epoxy group include an epoxy monomer having a bisphenol skeleton, an epoxy monomer having a dicyclopentadiene skeleton, an epoxy monomer having a naphthalene skeleton, an epoxy monomer having an adamantane skeleton, and an epoxy having a fluorene skeleton. Examples of the monomer include an epoxy monomer having a biphenyl skeleton, an epoxy monomer having a bi (glycidyloxyphenyl) methane skeleton, an epoxy monomer having a xanthene skeleton, an epoxy monomer having an anthracene skeleton, and an epoxy monomer having a pyrene skeleton. These hydrogenated products or modified products may be used. As for an epoxy compound (A1a), only 1 type may be used and 2 or more types may be used together.

Examples of the epoxy monomer having a bisphenol skeleton include an epoxy monomer having a bisphenol A type, bisphenol F type, or bisphenol S type bisphenol skeleton.

Examples of the epoxy monomer having a dicyclopentadiene skeleton include dicyclopentadiene dioxide and a phenol novolac epoxy monomer having a dicyclopentadiene skeleton.

Examples of the epoxy monomer having a naphthalene skeleton include 1-glycidylnaphthalene, 2-glycidylnaphthalene, 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidyl. Examples include naphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, and 1,2,5,6-tetraglycidylnaphthalene.

Examples of the epoxy monomer having an adamantane skeleton include 1,3-bis (4-glycidyloxyphenyl) adamantane and 2,2-bis (4-glycidyloxyphenyl) adamantane.

Examples of the epoxy monomer having a fluorene skeleton include 9,9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, and 9,9-bis (4- Glycidyloxy-3-chlorophenyl) fluorene, 9,9-bis (4-glycidyloxy-3-bromophenyl) fluorene, 9,9-bis (4-glycidyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-Glycidyloxy-3-methoxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dichlorophenyl) Fluorene and 9,9-bis (4-glycidyloxy-3,5-dibromophenyl) Fluorene, and the like.

Examples of the epoxy monomer having a biphenyl skeleton include 4,4'-diglycidylbiphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl.

Examples of the epoxy monomer having a bi (glycidyloxyphenyl) methane skeleton include 1,1′-bi (2,7-glycidyloxynaphthyl) methane, 1,8′-bi (2,7-glycidyloxynaphthyl) methane, 1,1′-bi (3,7-glycidyloxynaphthyl) methane, 1,8′-bi (3,7-glycidyloxynaphthyl) methane, 1,1′-bi (3,5-glycidyloxynaphthyl) methane 1,8'-bi (3,5-glycidyloxynaphthyl) methane, 1,2'-bi (2,7-glycidyloxynaphthyl) methane, 1,2'-bi (3,7-glycidyloxynaphthyl) And methane and 1,2′-bi (3,5-glycidyloxynaphthyl) methane.

Examples of the epoxy monomer having a xanthene skeleton include 1,3,4,5,6,8-hexamethyl-2,7-bis-oxiranylmethoxy-9-phenyl-9H-xanthene.

Specific examples of the oxetane compound (A1b) having an oxetanyl group include, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylate bis [(3- Ethyl-3-oxetanyl) methyl] ester, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, and oxetane-modified phenol novolac. As for an oxetane compound (A1b), only 1 type may be used and 2 or more types may be used together.

From the viewpoint of further improving the heat resistance of the cured product, the curable compound (A1) preferably has two or more cyclic ether groups.

From the viewpoint of further improving the heat resistance of the cured product, the content of the curable compound having two or more cyclic ether groups in 100% by weight of the curable compound (A1) is preferably 70% by weight or more. Preferably they are 80 weight% or more and 100 weight% or less. The content of the curable compound having two or more cyclic ether groups in the total 100% by weight of the curable compound (A1) may be 10% by weight or more and 100% by weight or less. Further, the entire curable compound (A1) may be a curable compound having two or more cyclic ether groups.

The molecular weight of the curable compound (A1) is less than 10,000. The molecular weight of the curable compound (A1) is preferably 200 or more, more preferably 1200 or less, still more preferably 600 or less, and particularly preferably 550 or less. When the molecular weight of the curable compound (A1) is not less than the above lower limit, the adhesiveness of the surface of the cured product is lowered, and the handleability of the curable composition is further enhanced. When the molecular weight of the curable compound (A1) is not more than the above upper limit, the adhesiveness of the cured product is further enhanced. Furthermore, the cured product is hard and hard to be brittle, and the adhesiveness of the cured product is further enhanced.

In the present specification, the molecular weight in the curable compound (A1) means a molecular weight that can be calculated from the structural formula when it is not a polymer and when the structural formula can be specified. Means weight average molecular weight.

Of the material of the insulating resin layer, 100% by weight of the material excluding the solvent and the inorganic filler (when the material of the insulating resin layer does not include the solvent and includes the inorganic filler, the insulating resin is included in 100% by weight of the material excluding the inorganic filler. When the layer material contains a solvent and does not contain an inorganic filler, the insulating resin layer material does not contain a solvent and does not contain an inorganic filler in 100% by weight of the material excluding the solvent. The content of the curable compound (A1) is preferably 10% by weight or more, more preferably 20% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less, and still more preferably 70% by weight. % By weight or less, particularly preferably 60% by weight or less, and most preferably 50% by weight or less. When the content of the curable compound (A1) is not less than the above lower limit, the adhesiveness and heat resistance of the cured product are further enhanced. When the content of the curable compound (A1) is not more than the above upper limit, the coating property at the production of the insulating resin layer is increased.

Curable compound (A2):
The curable compound (A2) is a curable compound having a molecular weight of 10,000 or more. The curable compound (A2) having a molecular weight of 10,000 or more is generally a polymer, and the molecular weight generally means a weight average molecular weight.

The curable compound (A2) preferably has an aromatic skeleton. In this case, the heat resistance of the cured product increases and the moisture resistance of the cured product also increases. In the case where the curable compound (A2) has an aromatic skeleton, the curable compound (A2) may have an aromatic skeleton in any part of the entire polymer, and has in the main chain skeleton. Or may be present in the side chain. From the viewpoint of further increasing the heat resistance of the cured product and further increasing the moisture resistance of the cured product, the curable compound (A2) preferably has an aromatic skeleton in the main chain skeleton. As for a sclerosing | hardenable compound (A2), only 1 type may be used and 2 or more types may be used together.

As the curable compound (A2), a curable resin such as a thermoplastic resin and a thermosetting resin can be used. The curable compound (A2) is preferably a thermoplastic resin or a thermosetting resin. The curable compound (A2) is preferably a curable resin. The curable compound (A2) is preferably a thermoplastic resin, and is preferably a thermosetting resin.

The thermoplastic resin and thermosetting resin are not particularly limited. The thermoplastic resin is not particularly limited, and examples thereof include styrene resin, phenoxy resin, phthalate resin, thermoplastic urethane resin, polyamide resin, thermoplastic polyimide resin, ketone resin, and norbornene resin. The thermosetting resin is not particularly limited, and examples thereof include amino resins, phenol resins, thermosetting urethane resins, epoxy resins, thermosetting polyimide resins, and amino alkyd resins. Examples of the amino resin include urea resin and melamine resin.

From the viewpoint of suppressing the oxidative deterioration of the cured product, further improving the heat cycle resistance and heat resistance of the cured product, and further reducing the water absorption rate of the cured product, the curable compound (A2) is a styrene resin, phenoxy. It is preferably a resin or an epoxy resin, more preferably a phenoxy resin or an epoxy resin, and even more preferably a phenoxy resin. In particular, use of a phenoxy resin or an epoxy resin further increases the heat resistance of the cured product. Moreover, use of a phenoxy resin further lowers the elastic modulus of the cured product and further improves the cold-heat cycle characteristics of the cured product. The curable compound (A2) may not have a cyclic ether group such as an epoxy group.

As the styrene resin, specifically, a homopolymer of a styrene monomer, a copolymer of a styrene monomer and an acrylic monomer, or the like can be used. Styrene polymers having a styrene-glycidyl methacrylate structure are preferred.

Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, pn- Butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2,4-dimethyl Examples include styrene and 3,4-dichlorostyrene.

The phenoxy resin is specifically a resin obtained by reacting, for example, an epihalohydrin and a divalent phenol compound, or a resin obtained by reacting a divalent epoxy compound and a divalent phenol compound.

The phenoxy resin has a bisphenol A skeleton, bisphenol F skeleton, bisphenol A / F mixed skeleton, naphthalene skeleton, fluorene skeleton, biphenyl skeleton, anthracene skeleton, pyrene skeleton, xanthene skeleton, adamantane skeleton or dicyclopentadiene skeleton. It is preferable. More preferably, the phenoxy resin has a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol A / F mixed skeleton, a naphthalene skeleton, a fluorene skeleton, or a biphenyl skeleton, and at least one of the fluorene skeleton and the biphenyl skeleton. More preferably, it has a skeleton. Use of the phenoxy resin having these preferable skeletons further increases the heat resistance of the cured product.

The epoxy resin is an epoxy resin other than the phenoxy resin. Examples of the epoxy resins include styrene skeleton-containing epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, biphenol type epoxy resins, naphthalene type epoxy resins, and fluorene type epoxy resins. , Phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, epoxy resin having adamantane skeleton, epoxy resin having tricyclodecane skeleton, and epoxy resin having triazine nucleus in skeleton Etc.

The molecular weight of the curable compound (A2) is 10,000 or more. The molecular weight of the curable compound (A2) is preferably 30000 or more, more preferably 40000 or more, preferably 1000000 or less, more preferably 250,000 or less. When the molecular weight of the curable compound (A2) is not less than the above lower limit, the cured product is hardly thermally deteriorated. When the molecular weight of the curable compound (A2) is not more than the above upper limit, the compatibility between the curable compound (A2) and other components is increased. As a result, the heat resistance of the cured product is further increased.

Of the material of the insulating resin layer, the content of the curable compound (A2) is preferably 20% by weight or more, more preferably 30% by weight or more, preferably 60% by weight in 100% by weight of the material excluding the solvent and inorganic filler. Hereinafter, it is more preferably 50% by weight or less. When the content of the curable compound (A2) is not less than the above lower limit, the handleability of the curable composition is improved. When the content of the curable compound (A2) is not more than the above upper limit, dispersion of the inorganic filler (C) becomes easy.

Curing agent (B):
The material of the insulating resin layer preferably contains a curing agent (B). As for a hardening | curing agent (B), only 1 type may be used and 2 or more types may be used together.

From the viewpoint of further improving the heat resistance of the cured product, the curing agent (B) preferably has an aromatic skeleton or an alicyclic skeleton. The curing agent (B) preferably includes an amine curing agent (amine compound), an imidazole curing agent, a phenol curing agent (phenol compound) or an acid anhydride curing agent (acid anhydride), and includes an amine curing agent. More preferred. The acid anhydride curing agent includes an acid anhydride having an aromatic skeleton, a water additive of the acid anhydride or a modified product of the acid anhydride, or an acid anhydride having an alicyclic skeleton, It is preferable to include a water additive of an acid anhydride or a modified product of the acid anhydride.

The curing agent (B) preferably contains a basic curing agent, a phenol resin having a melamine skeleton or a triazine skeleton, or a phenol resin having an allyl group. Furthermore, it is preferable that a hardening | curing agent (B) contains a basic hardening | curing agent from a viewpoint which makes the dispersibility of an inorganic filler (C) favorable, and also raises the voltage resistance and heat conductivity of hardened | cured material further. Further, from the viewpoint of further improving the dispersibility of the inorganic filler (C) and further enhancing the voltage resistance and thermal conductivity of the cured product, the curing agent (B) more preferably contains an amine curing agent. Preferably, dicyandiamide is included. The imidazole curing agent is also a kind of amine curing agent. Moreover, it is also preferable that a hardening | curing agent (B) contains both a dicyandiamide and an imidazole hardening | curing agent. By using these preferable curing agents, the dispersibility of the inorganic filler (C) in the curable composition is increased, and a cured product having an excellent balance of heat resistance, moisture resistance and electrical properties can be obtained. As a result, even if there is little content of an inorganic filler (C), thermal conductivity becomes quite high. In particular, when dicyandiamide is used, the adhesion between the cured product and the metal material becomes considerably high.

Whether the curing agent (B) is a basic curing agent is determined by placing 1 g of the curing agent in 10 g of a liquid containing 5 g of acetone and 5 g of pure water, and heating the mixture with stirring at 80 ° C. for 1 hour. Next, when an insoluble component in the liquid after heating is removed by filtration to obtain an extract, it is judged that the pH of the extract is basic.

Examples of the amine curing agent include dicyandiamide, imidazole compound, diaminodiphenylmethane, and diaminodiphenylsulfone. From the viewpoint of further improving the adhesion between the cured product and the metal material, the amine curing agent is more preferably a dicyandiamide or an imidazole curing agent. From the viewpoint of further improving the storage stability of the curable composition, the curing agent (B) preferably includes a curing agent having a melting point of 180 ° C. or higher, and includes an amine curing agent having a melting point of 180 ° C. or higher. It is more preferable.

Examples of the imidazole curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl. -2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2 '-Mech Imidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-Ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-dihydroxymethylimidazole, etc. Can be mentioned.

Examples of the phenol curing agent include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolak, xylylene modified novolak, decalin modified novolak, poly ( And di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, and poly (di-p-hydroxyphenyl) methane. From the viewpoint of further enhancing the flexibility of the cured product and the flame retardancy of the cured product, a phenol resin having a melamine skeleton, a phenol resin having a triazine skeleton, or a phenol resin having an allyl group is preferable.

Commercially available phenol curing agents include MEH-8005, MEH-8010 and MEH-8015 (all of which are manufactured by Meiwa Kasei Co., Ltd.), YLH903 (manufactured by Mitsubishi Chemical), LA-7052, LA-7054, and LA-7751. LA-1356 and LA-3018-50P (all of which are manufactured by DIC), and PS6313 and PS6492 (all of which are manufactured by Gunei Chemical Co., Ltd.).

Examples of the acid anhydride having an aromatic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride include, for example, a styrene / maleic anhydride copolymer, a benzophenone tetracarboxylic acid anhydride, and a pyromellitic acid anhydride. , Trimellitic anhydride, 4,4'-oxydiphthalic anhydride, phenylethynyl phthalic anhydride, glycerol bis (anhydrotrimellitate) monoacetate, ethylene glycol bis (anhydrotrimellitate), methyltetrahydroanhydride Examples include phthalic acid, methylhexahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride.

Examples of commercially available acid anhydrides having an aromatic skeleton, water additives of the acid anhydrides, or modified products of the acid anhydrides include SMA Resin EF30, SMA Resin EF40, SMA Resin EF60, and SMA Resin EF80 (any of the above Also manufactured by Sartomer Japan), ODPA-M and PEPA (all of which are manufactured by Manac), Ricacid MTA-10, Ricacid MTA-15, Ricacid TMTA, Ricacid TMEG-100, Ricacid TMEG-200, Ricacid TMEG-300, Ricacid TMEG-500, Ricacid TMEG-S, Ricacid TH, Ricacid HT-1A, Ricacid HH, Ricacid MH-700, Ricacid MT-500, Ricacid DSDA and Ricacid TDA-100 (all manufactured by Shin Nippon Rika) EPICLON B4400, EPICLON B650, and EPICLON B570 (all manufactured by both DIC Corporation).

The acid anhydride having an alicyclic skeleton, a water additive of the acid anhydride, or a modified product of the acid anhydride is an acid anhydride having a polyalicyclic skeleton, a water additive of the acid anhydride, or the A modified product of an acid anhydride, or an acid anhydride having an alicyclic skeleton obtained by addition reaction of a terpene compound and maleic anhydride, a water additive of the acid anhydride, or a modified product of the acid anhydride It is preferable. By using these curing agents, the flexibility of the cured product and the moisture resistance and adhesion of the cured product are further increased.

Examples of the acid anhydride having an alicyclic skeleton, a water addition of the acid anhydride, or a modified product of the acid anhydride include methyl nadic acid anhydride, acid anhydride having a dicyclopentadiene skeleton, and the acid anhydride And the like.

Examples of commercially available acid anhydrides having the alicyclic skeleton, water additions of the acid anhydrides, or modified products of the acid anhydrides include Ricacid HNA and Ricacid HNA-100 (all of which are manufactured by Shin Nippon Rika Co., Ltd.) , And EpiCure YH306, EpiCure YH307, EpiCure YH308H, EpiCure YH309 (all of which are manufactured by Mitsubishi Chemical Corporation) and the like.

The curing agent (B) is also preferably methyl nadic acid anhydride or trialkyltetrahydrophthalic anhydride. Use of methyl nadic anhydride or trialkyltetrahydrophthalic anhydride increases the water resistance of the cured product.

Of the material of the insulating resin layer, the content of the curing agent (B) is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 40% by weight in 100% by weight of the material excluding the solvent and inorganic filler. % Or less, more preferably 25% by weight or less. It is easy to fully harden a curable composition as content of a hardening | curing agent (B) is more than the said minimum. When the content of the curing agent (B) is not more than the above upper limit, it is difficult to generate an excessive curing agent (B) that does not participate in curing. For this reason, the heat resistance and adhesiveness of hardened | cured material become still higher.

(Inorganic filler (C))
By using the inorganic filler (C), the thermal conductivity of the cured product is considerably increased. As for an inorganic filler (C), only 1 type may be used and 2 or more types may be used together.

From the viewpoint of further increasing the thermal conductivity of the cured product, the thermal conductivity of the inorganic filler (C) is preferably 10 W / m · K or more, more preferably 15 W / m · K or more, and still more preferably 20 W / m ·. K or more. The upper limit of the thermal conductivity of the inorganic filler (C) is not particularly limited. Inorganic fillers having a thermal conductivity of about 300 W / m · K are widely known, and inorganic fillers having a thermal conductivity of about 200 W / m · K are easily available.

The inorganic filler (C) is preferably alumina, synthetic magnesite, boron nitride, aluminum nitride, silicon nitride, silicon carbide, zinc oxide or magnesium oxide, and alumina, boron nitride, aluminum nitride, silicon nitride, silicon carbide, Zinc oxide or magnesium oxide is more preferable. Use of these preferable inorganic fillers further increases the thermal conductivity of the cured product.

The inorganic filler (C) other than silica is more preferably spherical alumina, crushed alumina or spherical aluminum nitride, and even more preferably spherical alumina or spherical aluminum nitride. Use of these preferable inorganic fillers further increases the thermal conductivity of the cured product.

The new Mohs hardness of the inorganic filler (C) is preferably 12 or less, more preferably 9 or less. When the new Mohs hardness of the inorganic filler (C) is 9 or less, the workability of the cured product is further enhanced.

From the viewpoint of further improving the workability of the cured product, the inorganic filler (C) is preferably synthetic magnesite, crystalline silica, zinc oxide, or magnesium oxide. The new Mohs hardness of these inorganic fillers is 9 or less.

The inorganic filler (C) may contain a spherical filler (spherical filler), may contain a crushed filler (crushed filler), or may contain a plate-like filler (plate-like filler). Good. It is particularly preferable that the inorganic filler (C) includes a spherical filler. Since spherical fillers can be filled at high density, the use of spherical fillers further increases the thermal conductivity of the cured product.

Examples of the crushed filler include crushed alumina and crushed silica. The crushing filler is obtained, for example, by crushing a lump-like inorganic substance using a uniaxial crusher, a biaxial crusher, a hammer crusher, a ball mill, or the like. By using the crushed filler, the filler in the cured product tends to be bridged or effectively brought into a close structure. Therefore, the thermal conductivity of the cured product is further increased. Moreover, generally the crushing filler is cheap compared with a normal filler. For this reason, the cost of a curable composition becomes low by use of a crushing filler.

The silica is preferably crushed silica (crushed silica). By using the crushed silica, the moisture resistance of the cured product is further enhanced, and the voltage resistance is further unlikely to be lowered when the pressure cooker test of the cured product is performed.

The average particle size of the crushed filler is preferably 12 μm or less, more preferably 10 μm or less, and preferably 1 μm or more. When the average particle size of the crushed filler is not more than the above upper limit, the crushed filler can be dispersed with high density in the curable composition, and the withstand voltage of the cured product is further enhanced. When the average particle diameter of the crushed filler is not less than the above lower limit, it becomes easy to fill the crushed filler with high density.

The aspect ratio of the crushed filler is not particularly limited. The aspect ratio of the crushed filler is preferably 1.5 or more, and preferably 20 or less. Fillers with an aspect ratio of less than 1.5 are relatively expensive and increase the cost of the curable composition. When the aspect ratio is 20 or less, filling of the crushed filler is easy.

The aspect ratio of the crushed filler can be determined, for example, by measuring the crushed surface of the filler using a digital image analysis particle size distribution measuring device (“FPA” manufactured by Nippon Luft).

The average particle diameter of the inorganic filler (C) is preferably 0.1 μm or more, and preferably 40 μm or less. When the average particle diameter is not less than the above lower limit, the inorganic filler (C) can be easily filled at a high density. When the average particle size is not more than the above upper limit, the withstand voltage of the cured product is further enhanced.

The above-mentioned “average particle diameter” is an average particle diameter obtained from a volume average particle size distribution measurement result measured with a laser diffraction particle size distribution measuring apparatus.

Of the material of the insulating resin layer, 100% by weight of the material excluding the solvent (if the material of the insulating resin layer does not include the solvent, the material of the insulating resin layer includes the solvent in 100% by weight of the material of the insulating resin layer. In the case of 100% by weight of the material excluding the solvent) and 100% by weight of the insulating resin layer, the content of the inorganic filler (C) is preferably 50% by weight or more, more preferably 70% by weight or more, preferably 97 % By weight or less, more preferably 95% by weight or less. When the content of the inorganic filler (C) is not less than the above lower limit and not more than the above upper limit, the thermal conductivity of the cured product is effectively increased.

Other ingredients:
The material for the insulating resin layer may contain other components generally used for the insulating resin layer such as a dispersant, a chelating agent, and an antioxidant in addition to the components described above.

(First metal material and second metal material (metal material))
Examples of the material of the metal material include aluminum, copper, gold, and a graphite sheet. From the viewpoint of further improving thermal conductivity, the metal material is preferably gold, copper, or aluminum, and more preferably copper or aluminum. From the viewpoint of further improving the thermal conductivity and from the viewpoint of easily forming the etched metal material, the metal material is more preferably copper. The metal material is preferably a metal foil.

Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.

The following materials were prepared.

Curable compound (A1)
(1) Bisphenol A liquid epoxy resin ("Epicoat 828US" manufactured by Mitsubishi Chemical Corporation, Mw = 370)
(2) Bisphenol F type liquid epoxy resin (“Epicoat 806L” manufactured by Mitsubishi Chemical Corporation, Mw = 370)
(3) Naphthalene type liquid epoxy resin (“EPICLON HP-4032D” manufactured by DIC, Mw = 304)

Curable compound (A2)
(1) Epoxy group-containing styrene resin (“Marproof G-1010S” manufactured by NOF Corporation, Mw = 100,000, Tg = 93 ° C.)
(2) Bisphenol A type phenoxy resin (“E1256” manufactured by Mitsubishi Chemical Corporation, Mw = 51,000, Tg = 98 ° C.)

Curing agent (B)
(1) Alicyclic skeleton acid anhydride (“MH-700” manufactured by Shin Nippon Rika Co., Ltd.)
(2) Biphenyl skeleton phenolic resin (“MEH-7851-S” manufactured by Meiwa Kasei Co., Ltd.)
(3) Isocyanur-modified solid dispersion type imidazole (imidazole curing accelerator, “2MZA-PW” manufactured by Shikoku Kasei Kogyo Co., Ltd.)

Inorganic filler (C)
(1) 5 μm alumina (crushed alumina, “LT300C” manufactured by Nippon Light Metal Co., Ltd., average particle size 5 μm)
(2) Boron nitride (“MBN-010T” manufactured by Mitsui Chemicals, average particle size: 0.9 μm)
(3) Aluminum nitride (“MAN-2A” manufactured by Mitsui Chemicals, average particle size 1.3 μm)

Additives (1) Epoxysilane coupling agent (“KBE403” manufactured by Shin-Etsu Chemical Co., Ltd.)

Solvent (1) Methyl ethyl ketone

(Examples 1 to 16 and Comparative Examples 1 to 6)
Using a homodisper type stirrer, the blending components shown in Tables 1 to 3 below were blended in the blending amounts shown in Tables 1 to 3 below and kneaded to prepare an insulating material.

The above insulating material was applied to a release PET sheet (thickness 50 μm) to a target thickness, dried in an oven at 90 ° C. for 30 minutes, and the solvent was evaporated to prepare a sheet-like insulating material.

For Examples 1 to 9, 12 to 16, and Comparative Examples 1 to 6, the obtained sheet-like insulating material was laminated on a metal plate with a thermal laminator, and a laminate having a three-layer structure having an insulating resin layer was obtained. Produced. Thereafter, curing was performed at 180 ° C. for 1 hour to obtain a cured laminated structure. Then, the laminated body which has a predetermined area ratio was produced by etching the metal layer part of this laminated structure. For Examples 10 to 11, first, metal plates were fabricated by punching press processing so that the predetermined area and the front and back areas were the same. Thereafter, the metal plate and the sheet-like insulating material are bonded with a thermal laminator, and have a predetermined area ratio, and the area ratio between the insulating layer surface of the metal layer portion and the metal layer surface opposite to the insulating layer surface is the same. A laminate having a three-layer structure before curing was produced. Then, it hardened | cured at 180 degreeC for 1 hour, and the laminated body which has a predetermined area ratio and the same area ratio of the insulating layer surface of a metal layer part and the metal layer surface opposite to an insulating layer surface was produced.

(Evaluation)
(1) Measurement of thickness of each layer About the obtained laminated body, the cross section of the laminated body was observed and measured by the microscope ("VHX-5000" by Keyence Corporation), and the thickness of each layer was measured.

(2) Measurement of the surface area of the surface opposite to the insulating resin layer of the metal material The surface area was measured by observing the obtained laminate with an image size measuring instrument ("IM-6125" manufactured by Keyence Corporation).

(3) Measurement of glass transition temperature A sheet-like insulating material was cured at 180 ° C. for 1 hour to obtain a cured product (insulating resin layer).

The glass transition temperature of the obtained cured product was measured at a heating rate of 5 ° C./min using a dynamic viscoelasticity measuring device (“DMS6100” manufactured by Hitachi High-Tech Science Co., Ltd.).

(4) Measurement of elastic modulus The sheet-like insulating material was cured at 180 ° C. for 1 hour to obtain a cured product (insulating resin layer).

The elastic modulus of the cured product (insulating resin layer) was measured at 25 ° C. using a dynamic viscoelasticity measuring device (“DMS6100” manufactured by Hitachi High-Tech Science Co., Ltd.).

(5) Measurement of linear expansion coefficient The sheet-like insulating material was cured at 180 ° C. for 1 hour to obtain a cured product (insulating resin layer).

Using a thermomechanical analyzer (“TMA-60” manufactured by Shimadzu Corporation), the linear expansion coefficient of the cured product (insulating resin layer) and the first and second conditions under a condition between 25 ° C. and the glass transition temperature. The linear expansion coefficient of the metal material was measured.

(6) Measurement of arithmetic average roughness Ra In the obtained laminate, the arithmetic average roughness Ra of the surface opposite to the insulating resin layer side of the first metal material, the insulating resin layer side of the second metal material Arithmetic surface roughness Ra of the surface opposite to the surface, arithmetic average roughness Ra of the surface of the first metal material on the insulating resin layer side, and arithmetic average roughness of the surface of the second metal material on the insulating resin layer side Ra was measured.

Regarding a specific measuring method, the arithmetic average roughness Ra was measured at a moving speed of 0.6 mm using a surface roughness meter (“Surfcom Flex” manufactured by Tokyo Seimitsu Co., Ltd.).

(7) Measurement of thermal conductivity The sheet-like insulating material was cured at 180 ° C. for 1 hour to obtain a cured product (insulating resin layer).

The thermal conductivity of the cured product (insulating resin layer) was measured using a thermal conductivity meter (“Rapid Thermal Conductivity Meter QTM-500” manufactured by Kyoto Electronics Industry Co., Ltd.).

(8) Thermal resistance A heating element having the same size as the laminated body, controlled at 60 ° C., and having a smooth surface was prepared. The obtained laminate was pressed against the heating element at a pressure of 1 kgf, and the thermal resistance was evaluated by measuring the temperature of the opposite surface of the heating element with a thermocouple. Thermal resistance was determined according to the following criteria.

[Criteria of thermal resistance]
◯: Temperature difference between the heating element and the surface opposite to the heating element side of the laminate is 5 ° C. or less ○: Temperature difference between the heating element and the surface opposite to the heating element side of the laminate exceeds 5 ° C. 10 ° C or less Δ: Temperature difference between the heating element and the surface opposite to the heating element side of the laminate exceeds 10 ° C, and 30 ° C or less ×: Temperature difference between the heating element and the surface opposite to the heating element side of the laminate Over 30 ℃

(9) Anti-peeling property after cooling cycle 10 laminates obtained were subjected to 1000 cycles of cooling cycle test for 5 minutes at -40 ° C to 5 minutes at + 40 ° C with "Model TSB-51" manufactured by Espec. And by confirming the occurrence of peeling, the peeling prevention property after the thermal cycle was evaluated. The peel resistance after the cooling and heating cycle was determined according to the following criteria.

[Criteria for peeling prevention after cooling cycle]
○ ○: No floating or peeling occurred ○: 1 to 2 floating or separated occurrences △: 3 to 5 occurred floating or separated ×: 6 to 10 occurrences of floating or separated

Composition is shown in Tables 1 to 3 below. The configurations of the laminate and the evaluation results of the laminate are shown in Tables 4 to 6 below.

DESCRIPTION OF SYMBOLS 1,1A ... Laminated body 11 ... Insulating resin layer 12 ...

1st metal material

13, 13A ... 2nd metal material

Claims

An insulating resin layer;
A first metal material that is a metal foil or a metal plate;
A second metal material that is a metal foil or a metal plate,
The first metal material is laminated on the first surface of the insulating resin layer, and the second metal material is a second material opposite to the first surface of the insulating resin layer. Laminated on the surface,
The insulating resin layer has a thickness of 200 μm or less,
The total thickness of the first metal material and the second metal material is 200 μm or more,
The ratio of the thickness of the first metal material to the thickness of the second metal material is 0.2 or more and 5 or less,
The ratio of the surface area of the surface opposite to the insulating resin layer side of the first metal material to the surface area of the surface opposite to the insulating resin layer side of the second metal material is 0.5 or more, 2 A laminate that is:
The ratio of the linear expansion coefficient of the insulating resin layer to the linear expansion coefficient of the first metal material is 0.5 or more and 2 or less,
The laminate according to claim 1, wherein a ratio of a linear expansion coefficient of the insulating resin layer to a linear expansion coefficient of the second metal material is 0.5 or more and 2 or less.
The laminate according to claim 1 or 2, wherein the insulating resin layer has an elastic modulus at 25 ° C of 1 GPa or more and 50 GPa or less.
The laminate according to any one of claims 1 to 3, wherein a side surface of the first metal material is inclined inwardly toward a surface side opposite to the insulating resin layer side.
The laminate according to any one of claims 1 to 4, wherein a side surface of the second metal material is inclined inwardly toward the surface side opposite to the insulating resin layer side.
The laminate according to any one of claims 1 to 5, wherein the first metal material is a circuit.
There is an insulating resin layer portion on which the first metal material is not laminated,
The arithmetic average roughness Ra of the surface opposite to the insulating resin layer side of the first metal material is 2 μm or less, and the arithmetic average roughness Ra of the surface of the first metal material on the insulating resin layer side is The laminate according to any one of claims 1 to 6, which is 0.1 µm or more.
The ratio of the surface area of the surface opposite to the insulating resin layer side of the first metal material to the surface area of the surface of the first metal material on the insulating resin layer side is 0.8 or more and less than 1.0. The laminate according to any one of claims 1 to 7, wherein
The first metal material is a circuit;
The laminate according to any one of claims 1 to 8, wherein the second metal material is a circuit.
There is an insulating resin layer portion where the second metal material is not laminated,
The arithmetic average roughness Ra of the surface opposite to the insulating resin layer side of the second metal material is 2 μm or less, and the arithmetic average roughness Ra of the surface of the second metal material on the insulating resin layer side is The laminate according to any one of claims 1 to 9, which is 0.1 袖 m or more.
The ratio of the surface area of the surface opposite to the insulating resin layer side of the second metal material to the surface area of the surface of the second metal material on the insulating resin layer side is 0.8 or less. The laminate according to any one of 1 to 10.
The laminate according to any one of claims 1 to 11, wherein the glass transition temperature of the insulating resin layer is 150 ° C or higher.
The laminate according to any one of claims 1 to 12, wherein the insulating resin layer is not a prepreg.
The surface of the first metal material opposite to the insulating resin layer side is exposed, or a protective film is laminated on the surface of the first metal material opposite to the insulating resin layer side. The laminate according to any one of claims 1 to 13, wherein
The laminate according to any one of claims 1 to 14, wherein a surface of the first metal material opposite to the insulating resin layer side is exposed.
The laminate according to any one of claims 1 to 15, wherein the insulating resin layer contains an inorganic filler.